CN107400898A - A kind of synthetic method of 2 pyridine carboxylic acid methyl esters - Google Patents
A kind of synthetic method of 2 pyridine carboxylic acid methyl esters Download PDFInfo
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Abstract
The invention discloses a kind of synthetic method of 2 pyridine carboxylic acid methyl esters, this method by 2 bromopyridines withN,NDimethylformamide or acetonitrile and etamon chloride or tetraethylammonium bromide or tetraethyl ammonium iodide or tetraethyl tetrafluoro boric acid amine or tetrabutylammonium chloride or TBAB or tetrabutylammonium iodide are mixed into electrolyte, lead to carbon dioxide 30min at ambient pressure, electric carboxylation reaction is then carried out with constant current（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, then through being esterified, post-processing and obtaining 2 pyridine carboxylic acid methyl esters；Reaction system of the present invention is simple, easily-controllable, and with abundant C1 resources CO2As one of raw material, raw material is cheap and easy to get, and cost is low, and the research for organic matters such as challenging green syt heterocyclic carboxylic acid derivatives opens a new way.
Description
Technical field
The present invention relates to electrochemistry technical field of organic synthesis, more particularly, to a kind of synthesis side of 2- pyridine carboxylic acids methyl esters
Method.
Background technology
Carbon dioxide is main greenhouse gases, and being fixed to utilize has great importance.In recent years, with electrochemistry side
The fixed carbon dioxide of method activation is increasingly closed for the electric carboxylation reaction of all kinds of chemicals with economic competitiveness by people
Note, and it is the most effective of utility that the carboxylation reaction of the compound of the key containing C-X and carbon dioxide, which is effective fixed carbon dioxide,
One of method.In nearest decades, the electric carboxylation research on halides has been reported.The complexs such as cobalt, nickel, palladium are used as and urged
Agent can effectively improve the corresponding reduzate yield of organic halogen.
2- pyridine carboxylic acid methyl esters is important fine chemicals and medicine and material intermediate.Singh et al. is in S.K.
In Singh, M.S. Reddy, M. Mangle, K.R. Ganesh, Tetrahedron 63 (2007) 126-130,
Kobayashi et al. is in H. Miyamura, T. Yasukawa, S. Kobayashi, Green Chem. 12 (2010)
In 776-778, Boydston et al. is in E.E. Finney, K.A. Ogawa, A.J. Boydston, J. Am. Chem.
Soc. in 134 (2012) 12,374 12377 and Bhanage et al. is in R.S. Mane, T. Sasakib, B.M.
The synthesis of 2- pyridine carboxylic acid methyl esters is have studied in Bhanage, RSC Adv. 5 (2015) 94,776 94785, but is reacted
In be required to applications catalyst, made troubles to purification of products.Meanwhile Albaneze-Walker et al. is in J. Albaneze-
Walker, C. Bazaral, T. Leavey, P.G. Dormer, J.A. Murry, Org. Lett. 6 (2004)
Also studied the synthesis of 2- pyridine carboxylic acid methyl esters in 2097-2100, however needed in reacting using poisonous gas carbon monoxide and
Experiment needs to carry out at high temperature under high pressure.In addition, Okimoto et al. is in M. Okimoto, Y. Nagata, S. Sueda,
Y. have studied 1,2- diketone electrochemistry in Takahashi, Synthetic. Commun. 33 (2003) 3771-3776
It is oxidized to 2- pyridine carboxylic acid methyl esters.
So far, also not on the research of 2- bromopyridines electrochemical reduction and report in carbon dioxide atmosphere.2-
Bromopyridine is that the ortho position of N atoms on pyridine ring has connected a C-Br key, and C-Br keys are not general easily-activated, and activation potential is higher.This
Literary Applied Electrochemistry technology, 2- bromopyridines are electrolysed under carbon dioxide atmosphere, C-Br keys has been activated while has introduced COO–, synthesis
Corresponding carboxylation product 2- pyridine carboxylic acid methyl esters.Both effectively fixation make use of CO to this method2, while also synthesized important become more meticulous
Product and medicine and material intermediate.
The content of the invention
A kind of synthetic method for 2- pyridine carboxylic acids methyl esters that the purpose of the present invention is in view of the shortcomings of the prior art and provided,
It is using the heterocycle halides containing a C-Br key as reaction substrate, in CO2Under atmosphere, corresponding carboxylation product 2- pyridine first is generated
Sour methyl esters, reaction system is simple, easily-controllable, and with abundant C1 resources CO2Cheap and easy to get as one of raw material, cost is low, no
Environment is polluted, is a kind of process route for having very much commercial synthesis to be worth.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of synthetic method of 2- pyridine carboxylic acids methyl esters, this method by 2- bromopyridines withN,N- dimethylformamide or acetonitrile and four
Ethyl ammonium chloride or tetraethylammonium bromide or tetraethyl ammonium iodide or tetraethyl tetrafluoro boric acid amine or tetrabutylammonium chloride or four fourths
Base ammonium bromide or tetrabutylammonium iodide are mixed into electrolyte, lead to the min of carbon dioxide 30 at ambient pressure, are then carried out with constant current
Electric carboxylation reaction（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, then through being esterified, post-processing and obtaining 2- pyridine carboxylic acids
Methyl esters, comprise the following steps that：
A, the preparation of electrolyte；B, electric carboxylation reaction；C, esterification；D, rotate；E, detect.
Preferred scheme is that the a's comprises the following steps that：By 2- bromopyridines withN,N- dimethylformamide or acetonitrile and four
Ethyl ammonium chloride or tetraethylammonium bromide or tetraethyl ammonium iodide or tetraethyl tetrafluoro boric acid amine or tetrabutylammonium chloride or four fourths
Base ammonium bromide or tetrabutylammonium iodide press 1:129:1 mixed in molar ratio into electrolyte, be then placed in negative electrode for stainless steel or copper or
Silver or platinum or nickel or titanium or glass carbon and anode is in a Room type electrolytic cells of magnesium rod.
Preferred scheme is that the b's comprises the following steps that：Under normal pressure, the min of carbon dioxide 30 is led into above-mentioned electrolytic cell,
Then with 3 ~ 18 mA/cm2（Preferable 13 mA/cm2）Constant current density be electrolysed（Electrolytic process one leads directly to carbon dioxide
Terminate to electrolysis）, its reaction temperature is -20 ~ 25 DEG C（Preferably 0 DEG C）, turn on angle is every mole of 1.0 ~ 6.0 F of 2- bromopyridines
（Preferably 2.5 F）, F is Faraday constant.
Preferred scheme is that the c's comprises the following steps that：After cell reaction terminates, above-mentioned electrolytic liquid body is all moved
Enter round-bottomed flask, according to every 1 ml electrolyte add 0.03 g Anhydrous potassium carbonates and 0.03 mL analyze the ratio of pure iodomethane to
Anhydrous potassium carbonate and iodomethane are added in flask, at 50~60 DEG C of temperature, is stirred at reflux 5 hours progress esterifications, instead
Hydrochloric acid is added dropwise after should terminating to neutralize, the electrolytic liquid body pH value for making esterification is about 7, and its Anhydrous potassium carbonate and iodomethane are analysis
It is pure.
Preferred scheme is that the d's comprises the following steps that：The electrolytic liquid body of above-mentioned esterification and ether are pressed 1：2 body
Product than extraction three times, is dehydrated and filtered with anhydrous magnesium sulfate after merging organic layer, and filtrate is depressurized by normal temperature（Pressure is 0.1
MPa）The crude product of 2- pyridine carboxylic acid methyl esters is obtained after revolving removing absolute ether.
Preferred scheme is that the e's comprises the following steps that：Use gas phase（GC）Detect products collection efficiency.
The present invention has the advantages of method is simple, easy to operate, safe compared with prior art, can be to the gas of greenhouse effects
Body carbon dioxide is effectively utilized, and greatly reduces atmosphere pollution, has very great meaning to environmental protection.
The conversion of pyridine halides is realized simultaneously, and 2- pyridine carboxylic acid methyl esters is effectively synthesized, and raw material is cheap and easy to get, cost
Low, the research for organic matters such as challenging green syt heterocyclic carboxylic acid derivatives opens a new way, 2- pyridines
Methyl formate is good Organic Chemicals, has important use in chemical industry and pharmaceuticals industry；Synthesized in materials chemistry product
Field shows fabulous application prospect, is a kind of process route for having very much commercial synthesis to be worth.
Embodiment
The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are served only for
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made to the present invention according to the invention described above content.
It is raw materials used such as 2- bromopyridines, tetraethylammonium bromide, N,N-dimethylformamide, tetrabutyl bromine wherein in embodiment
Change ammonium etc. and be purchased from lark prestige Co., Ltd or Chinese medicines group.
A kind of synthetic method of 2- pyridine carboxylic acids methyl esters of embodiment 1, is comprised the following steps that：
A, the preparation of electrolyte
By 1mmol（95 ul）2- bromopyridines and 1 mmol（0.2102 g）Tetraethylammonium bromide and 0.129 mol（10 mL）N, N- dimethylformamide is mixed into electrolyte, and it is negative electrode and magnesium rod as in a Room type electrolytic cell of anode to be then placed in using silver, 2-
Bromopyridine, tetraethylammonium bromide andN,N- dimethylformamide is pure to analyze, wherein：2- bromopyridines are substrate,N,N- dimethyl
Formamide is 4 grades of dried solvents of molecular sieve, and tetraethylammonium bromide is supporting electrolyte；
B, electric carboxylation reaction
Under normal pressure, the min of carbon dioxide 30 is passed through into above-mentioned electrolytic cell, then with 8 mA/cm2Constant current density carry out electricity
Solution（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, its turn on angle is 193 C, and its reaction temperature is 0 DEG C, turn on angle
With 2.0 F, F it is Faraday constant for every mole of 2- bromopyridine；
C, esterification
After cell reaction terminates, above-mentioned electrolytic liquid body is all moved into round-bottomed flask, 0.03 is added according to every 1 ml electrolyte
The ratio that g Anhydrous potassium carbonates and 0.03 mL analyze pure iodomethane adds Anhydrous potassium carbonate and iodomethane into flask, in temperature 55
At DEG C, 5 hours progress esterifications are stirred at reflux, reaction is added dropwise hydrochloric acid after terminating and neutralized, and makes the electrolytic liquid body pH of esterification
Value about 7, its Anhydrous potassium carbonate and iodomethane are pure to analyze；
D, rotate
The electrolytic liquid body of above-mentioned esterification and ether are pressed 1：2 volume ratio extraction three times, anhydrous slufuric acid is used after merging organic layer
Magnesium is dehydrated and filtered, and filtrate is depressurized by normal temperature（Pressure is 0.1 MPa）2- pyridine carboxylic acid first is obtained after revolving removing absolute ether
The crude product of ester；
E, detect
Use gas phase（GC）Product is detected, 2- pyridine carboxylic acid methyl esters yield is 22.4%.
A kind of synthetic method of 2- pyridine carboxylic acids methyl esters of embodiment 2, is comprised the following steps that：
A, the preparation of electrolyte
By 1 mmol（95 ul ）2- bromopyridines and 1 mmol（0.3224 g）TBAB and 0.129 mol（10 mL）N,N- dimethylformamide is mixed into electrolyte, and it is the Room type electrolytic cell of negative electrode and magnesium rod as anode to be then placed in using silver strip
It is interior, 2- bromopyridines, TBAB andN,N- dimethylformamide is pure to analyze, wherein：2- bromopyridines are substrate,N,N- two
NMF is 4 grades of dried solvents of molecular sieve, and TBAB is supporting electrolyte；
B, electric carboxylation reaction
Under normal pressure, the min of carbon dioxide 30 is passed through into above-mentioned electrolytic cell, then with 8 mA/cm2Constant current density carry out electricity
Solution（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, its turn on angle is 193 C, and its reaction temperature is 0 DEG C, turn on angle
With 2.0 F, F it is Faraday constant for every mole of 2- bromopyridine；
C, esterification
After cell reaction terminates, above-mentioned electrolytic liquid body is all moved into round-bottomed flask, 0.03 is added according to every 1 ml electrolyte
The ratio that g Anhydrous potassium carbonates and 0.03 mL analyze pure iodomethane adds Anhydrous potassium carbonate and iodomethane into flask, in temperature 55
At DEG C, 5 hours progress esterifications are stirred at reflux, reaction is added dropwise hydrochloric acid after terminating and neutralized, and makes the electrolytic liquid body pH of esterification
Value about 7, its Anhydrous potassium carbonate and iodomethane are pure to analyze；
D, rotate
The electrolytic liquid body of above-mentioned esterification and ether are pressed 1：2 volume ratio extraction three times, anhydrous slufuric acid is used after merging organic layer
Magnesium is dehydrated and filtered, and filtrate is depressurized by normal temperature（Pressure is 0.1 MPa）2- pyridine carboxylic acid first is obtained after revolving removing absolute ether
The crude product of ester；
E, detect
Use gas phase（GC）Product is detected, 2- pyridine carboxylic acid methyl esters yield is 28.6%.
A kind of synthetic method of 2- pyridine carboxylic acids methyl esters of embodiment 3, is comprised the following steps that：
By 1mmol（95 ul ）2- bromopyridines and 1 mmol（0.3224 g）TBAB and 0.129 mol（10 mL）N,N- dimethylformamide is mixed into electrolyte, and it is negative electrode and magnesium rod as in a Room type electrolytic cell of anode to be then placed in using nickel,
2- bromopyridines, TBAB andN,N- dimethylformamide is pure to analyze, wherein：2- bromopyridines are substrate,N,N- diformazan
Base formamide is 4 grades of dried solvents of molecular sieve, and TBAB is supporting electrolyte；
B, electric carboxylation reaction
Under normal pressure, the min of carbon dioxide 30 is passed through into above-mentioned electrolytic cell, then with 8 mA/cm2Constant current density carry out electricity
Solution（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, its turn on angle is 193 C, and its reaction temperature is 0 DEG C, turn on angle
With 2.0 F, F it is Faraday constant for every mole of 2- bromopyridine；
C, esterification
After cell reaction terminates, above-mentioned electrolytic liquid body is all moved into round-bottomed flask, 0.03 g is added according to every 1ml electrolyte
The ratio that Anhydrous potassium carbonate and 0.03 mL analyze pure iodomethane adds Anhydrous potassium carbonate and iodomethane into flask, in temperature 55
At DEG C, 5 hours progress esterifications are stirred at reflux, reaction is added dropwise hydrochloric acid after terminating and neutralized, and makes the electrolytic liquid body pH of esterification
Value about 7, its Anhydrous potassium carbonate and iodomethane are pure to analyze；
D, rotate
The electrolytic liquid body of above-mentioned esterification and ether are pressed 1：2 volume ratio extraction three times, anhydrous slufuric acid is used after merging organic layer
Magnesium is dehydrated and filtered, and filtrate is depressurized by normal temperature（Pressure is 0.1 MPa）2- pyridine carboxylic acid first is obtained after revolving removing absolute ether
The crude product of ester；
E, detect
Use gas phase（GC）Product is detected, 2- pyridine carboxylic acid methyl esters yield is 18.9%.
A kind of synthetic method of 2- pyridine carboxylic acids methyl esters of embodiment 4, is comprised the following steps that：
A, the preparation of electrolyte
By 1 mmol（95 ul ）2- bromopyridines and 1 mmol（0.3224 g）TBAB and 0.129 mol（10 mL）N,N- dimethylformamide is mixed into electrolyte, and it is negative electrode and magnesium rod as in a Room type electrolytic cell of anode to be then placed in using copper,
2- bromopyridines, TBAB andN,N- dimethylformamide is pure to analyze, wherein：2- bromopyridines are substrate,N,N- diformazan
Base formamide is 4 grades of dried solvents of molecular sieve, and TBAB is supporting electrolyte；
B, electric carboxylation reaction
Under normal pressure, the min of carbon dioxide 30 is passed through into above-mentioned electrolytic cell, then with 8 mA/cm2Constant current density carry out electricity
Solution（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, its turn on angle is 193 C, and its reaction temperature is 0 DEG C, turn on angle
With 2.0 F, F it is Faraday constant for every mole of 2- bromopyridine；
C, esterification
After cell reaction terminates, above-mentioned electrolytic liquid body is all moved into round-bottomed flask, 0.03 is added according to every 1 ml electrolyte
The ratio that g Anhydrous potassium carbonates and 0.03mL analyze pure iodomethane adds Anhydrous potassium carbonate and iodomethane into flask, in temperature 55
At DEG C, 5 hours progress esterifications are stirred at reflux, reaction is added dropwise hydrochloric acid after terminating and neutralized, and makes the electrolytic liquid body pH of esterification
Value about 7, its Anhydrous potassium carbonate and iodomethane are pure to analyze；
D, rotate
The electrolytic liquid body of above-mentioned esterification and ether are pressed 1：2 volume ratio extraction three times, anhydrous slufuric acid is used after merging organic layer
Magnesium is dehydrated and filtered, and filtrate is depressurized by normal temperature（Pressure is 0.1 MPa）2- pyridine carboxylic acid first is obtained after revolving removing absolute ether
The crude product of ester；
E, detect
Use gas phase（GC）Product is detected, 2- pyridine carboxylic acid methyl esters yield is 16.7%.
A kind of synthetic method of 2- pyridine carboxylic acids methyl esters of embodiment 5, is comprised the following steps that：
A, the preparation of electrolyte
By 1 mmol（95 ul ）2- bromopyridines and 1 mmol（0.3224 g）TBAB and 0.129 mol（10 mL）N,N- dimethylformamide is mixed into electrolyte, and it is negative electrode and magnesium rod as in a Room type electrolytic cell of anode to be then placed in using silver,
2- bromopyridines, TBAB andN,N- dimethylformamide is pure to analyze, wherein：2- bromopyridines are substrate,N,N- diformazan
Base formamide is 4 grades of dried solvents of molecular sieve, and TBAB is supporting electrolyte；
B, electric carboxylation reaction
Under normal pressure, the min of carbon dioxide 30 is passed through into above-mentioned electrolytic cell, then with 13 mA/cm2Constant current density carry out electricity
Solution（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, its turn on angle is 241 C, and its reaction temperature is 0 DEG C, turn on angle
With 2.5 F, F it is Faraday constant for every mole of 2- bromopyridine；
C, esterification
After cell reaction terminates, above-mentioned electrolytic liquid body is all moved into round-bottomed flask, 0.03 is added according to every 1 ml electrolyte
The ratio that g Anhydrous potassium carbonates and 0.03 mL analyze pure iodomethane adds Anhydrous potassium carbonate and iodomethane into flask, in temperature 55
At DEG C, 5 hours progress esterifications are stirred at reflux, reaction is added dropwise hydrochloric acid after terminating and neutralized, and makes the electrolytic liquid body pH of esterification
Value about 7, its Anhydrous potassium carbonate and iodomethane are pure to analyze；
D, rotate
The electrolytic liquid body of above-mentioned esterification and ether are pressed 1：2 volume ratio extraction three times, anhydrous slufuric acid is used after merging organic layer
Magnesium is dehydrated and filtered, and filtrate is depressurized by normal temperature（Pressure is 0.1 MPa）2- pyridine carboxylic acid first is obtained after revolving removing absolute ether
The crude product of ester；
E, detect
Use gas phase（GC）Product is detected, 2- pyridine carboxylic acid methyl esters yield is 37.4%.
A kind of synthetic method of 2- pyridine carboxylic acids methyl esters of embodiment 6, is comprised the following steps that：
A, the preparation of electrolyte
By 1 mmol（95 ul ）2- bromopyridines and 1 mmol（0.3224 g）TBAB and 0.129 mol（10 mL）N,N- dimethylformamide is mixed into electrolyte, and it is negative electrode and magnesium rod as in a Room type electrolytic cell of anode to be then placed in using silver,
2- bromopyridines, TBAB andN,N- dimethylformamide is pure to analyze, wherein：2- bromopyridines are substrate,N,N- diformazan
Base formamide is 4 grades of dried solvents of molecular sieve, and TBAB is supporting electrolyte；
B, electric carboxylation reaction
Under normal pressure, the min of carbon dioxide 30 is passed through into above-mentioned electrolytic cell, then with 13 mA/cm2Constant current density carry out electricity
Solution（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, its turn on angle is 241 C, and its reaction temperature is -5 DEG C, is powered
It is Faraday constant to measure as every mole of 2- bromopyridine with 2.5 F, F；
C, esterification
After cell reaction terminates, above-mentioned electrolytic liquid body is all moved into round-bottomed flask, 0.03 is added according to every 1 ml electrolyte
The ratio that g Anhydrous potassium carbonates and 0.03 mL analyze pure iodomethane adds Anhydrous potassium carbonate and iodomethane into flask, in temperature 55
At DEG C, 5 hours progress esterifications are stirred at reflux, reaction is added dropwise hydrochloric acid after terminating and neutralized, and makes the electrolytic liquid body pH of esterification
Value about 7, its Anhydrous potassium carbonate and iodomethane are pure to analyze；
D, rotate
The electrolytic liquid body of above-mentioned esterification and ether are pressed 1：2 volume ratio extraction three times, anhydrous slufuric acid is used after merging organic layer
Magnesium is dehydrated and filtered, and filtrate is depressurized by normal temperature（Pressure is 0.1 MPa）2- pyridine carboxylic acid first is obtained after revolving removing absolute ether
The crude product of ester；
E, detect
Use gas phase（GC）Product is detected, 2- pyridine carboxylic acid methyl esters yield is 33.6%.
It is 2- pyridine carboxylic acid methyl esters that above-mentioned each case study on implementation products therefrom is can confirm that after analysis（English name：Methyl
picolinate）, its molecular formula is C7H7NO2, molecular weight 137.14, structural formula is as follows：
Simply the present invention will be further described for various embodiments above, and is not used to limit patent of the present invention, all to be of the invention
Equivalence enforcement, it is intended to be limited solely by within the right of patent of the present invention.
Thank to state natural sciences fund（21503104）, Shandong Province's Natural Science Fund In The Light（ZR2014BQ010）, Liaocheng City
Development in science and technology plan fund（2014GJH08）And Liaocheng University high-level personnel and doctor's scientific research initial funding（31805）To this
The subsidy of project.
Claims (6)
- A kind of 1. synthetic method of 2- pyridine carboxylic acids methyl esters, it is characterised in that this method by 2- bromopyridines withN,N- dimethyl methyl Acid amides or acetonitrile and etamon chloride or tetraethylammonium bromide or tetraethyl ammonium iodide or tetraethyl tetrafluoro boric acid amine or four fourths Ammonium chloride or TBAB or tetrabutylammonium iodide are mixed into electrolyte, lead to the min of carbon dioxide 30 at ambient pressure, so Electric carboxylation reaction is carried out with constant current afterwards（Electrolytic process is passed through carbon dioxide to electrolysis always to be terminated）, then through esterification, after locate 2- pyridine carboxylic acid methyl esters is managed to obtain, is comprised the following steps that：A, the preparation of electrolyte；B, electric carboxylation reaction；C, esterification；D, rotate；E, detect.
- A kind of 2. synthetic method of 2- pyridine carboxylic acids methyl esters as claimed in claim 1, it is characterised in that the specific step of a It is rapid as follows：By 2- bromopyridines withN,N- dimethylformamide or acetonitrile and etamon chloride or tetraethylammonium bromide or tetraethyl Ammonium iodide or tetraethyl tetrafluoro boric acid amine or tetrabutylammonium chloride or TBAB or tetrabutylammonium iodide press 1:129:1 rubs Your ratio is mixed into electrolyte, is then placed in that negative electrode is stainless steel or copper or silver or platinum or nickel or titanium or glass carbon and anode is magnesium rod In one Room type electrolytic cell.
- A kind of 3. synthetic method of 2- pyridine carboxylic acids methyl esters as claimed in claim 1, it is characterised in that the specific step of the b It is rapid as follows：Under normal pressure, the min of carbon dioxide 30 is led into above-mentioned electrolytic cell, then with 3 ~ 18 mA/cm2（Preferable 13 mA/ cm2）Constant current density be electrolysed（Electrolytic process one, which leads directly to carbon dioxide to electrolysis, to be terminated）, its reaction temperature is -20 ~ 25 ℃（Preferably 0 DEG C）, turn on angle is every mole of 1.0 ~ 6.0 F of 2- bromopyridines（Preferably 2.5F）, F is Faraday constant.
- A kind of 4. synthetic method of 2- pyridine carboxylic acids methyl esters as claimed in claim 1, it is characterised in that the specific step of the c It is rapid as follows：After cell reaction terminates, above-mentioned electrolytic liquid body is all moved into round-bottomed flask, added according to every 1 ml electrolyte The ratio that 0.03 g Anhydrous potassium carbonates and 0.03 mL analyze pure iodomethane adds Anhydrous potassium carbonate and iodomethane into flask, At 50~60 DEG C of temperature, 5 hours progress esterifications are stirred at reflux, reaction is added dropwise hydrochloric acid after terminating and neutralized, and makes the electricity of esterification Liquid pH value is about 7 after solution, and its Anhydrous potassium carbonate and iodomethane are pure to analyze.
- A kind of 5. synthetic method of 2- pyridine carboxylic acids methyl esters as claimed in claim 1, it is characterised in that the specific step of the d It is rapid as follows：The electrolytic liquid body of above-mentioned esterification and ether are pressed 1：2 volume ratio extracts three times, with anhydrous sulphur after merging organic layer Sour magnesium is dehydrated and filtered, and filtrate is depressurized by normal temperature（Pressure is 0.1 MPa）2- pyridine carboxylic acids are obtained after revolving removing absolute ether The crude product of methyl esters.
- A kind of 6. synthetic method of 2- pyridine carboxylic acids methyl esters as claimed in claim 1, it is characterised in that the specific step of the e It is rapid as follows：Use gas phase（GC）Detect products collection efficiency.
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| CN108977839A (en) * | 2018-08-17 | 2018-12-11 | 聊城大学 | A kind of synthetic method of 4-thiazolecarboxylic acid |
| CN112048734A (en) * | 2020-09-11 | 2020-12-08 | 四川大学 | Regioselective electrochemical synthesis method of nitrogen-containing aromatic heterocyclic carboxylic acid |
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| CN108977839B (en) * | 2018-08-17 | 2020-08-11 | 聊城大学 | Synthesis method of thiazole-4-formic acid |
| CN112048734A (en) * | 2020-09-11 | 2020-12-08 | 四川大学 | Regioselective electrochemical synthesis method of nitrogen-containing aromatic heterocyclic carboxylic acid |
| CN112048734B (en) * | 2020-09-11 | 2022-06-10 | 四川大学 | Regioselective electrochemical synthesis method of nitrogen-containing aromatic heterocyclic carboxylic ester |
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